The present invention is directed to compositions and methods for forming certain golf equipment, such as golf shoes, golf clubs, golf gloves, or portions thereof having improved properties with the subject compositions. The compositions of the invention comprise at least one ionomer formed from a sulfonated polymer, a phosphonated polymer, or a carboxylated polymer, their precursors, or a combination thereof.
It is well known to even the average golfer that the equipment used in playing the game is subject to a great deal of friction, impact, and other stresses during a typical round of golf. Both the performance and the useful life of such equipment would benefit from the use of materials having improved resilience, dimensional stability, and increased durability. For instance, many types of golf clubs, such as putters, drivers, and wedges, contain polymer inserts in the face of the club. Obviously, since the club face directly strikes a golf ball thousands of times over the life of the club, improved resilience and durability are of great importance. Additionally, club components, such as shafts, grips, and hosels, undergo significant stress during a golf swing and contact with a golf ball and, therefore, could stand to benefit from more durable materials.
Another example is golf gloves, which undergo a lot of friction and wear and tear during a round of golf, not only from contact with, and friction from, golf club grips, but also from weather-related causes, such as excess moisture, heat, and ultraviolet radiation. Liners and, more specifically, polymer-reinforced liners (inner or outer liners), that are constructed of a more durable material, might provide a significant improvement in glove durability. Shoes are another type of golf equipment that receive a lot of stress and friction during a round (or multiple rounds) of golf. Shoe soles are flexed thousands of times per round and hundreds of thousands of times over the life of the shoe, as are the foot-beds and liners inside the shoes. Polymer or plastic spikes are, obviously, repetitively driven into, and scraped against cart paths, pavement, hard ground, and many other types of hard surfaces routinely encountered on golf courses.
Other types of golf equipment that require increased durability include various types of golf carts and course maintenance vehicles, golf bags and their associated framework, support legs and stands, golf tees, and fabrics designed for the potentially harsh (sun, rain, wind, hail, etc.) environments encountered by many golfers throughout the many seasons during which golf is played.
Golf equipment is typically formulated from a variety of different materials. One type of commonly employed polymer are ionomers of an ethylene-methacrylic acid neutralized by a metal ion. However, these conventional ionomeric materials do not entirely solve the problems associated with stress, durability, and repeated impact, as described above. Therefore, it is clear that improved materials, having material properties that address these preferred physical requirements, are necessary.
A handful of references are directed to golf equipment, such as golf clubs, having ionomer resins as part of their construction. U.S. Pat. No. 4,809,978 discloses a golf club head of a wood-type or an iron-type having a face plate formed of an ionomer resin having a Young""s modulus in the range of 20 to 50 kg/mm2. The thermoplastic ionomer resin is based on ethylene-methacrylic acid neutralized by a metal ion.
U.S. Pat. No. 4,204,684 discloses a golf club head and method of producing the same, wherein the head is fashioned of laminations or layers of resinous or plastic materials bonded together to form an integrated or composite head or body. The laminates are constructed of ethylene-methacrylic acid ionomers neutralized with a metal ion or polyamide resin.
U.S. Pat. Nos. 5,465,969 and 5,507,985 each disclose a golf club having a hollow metal head defining a cavity filled with a thermoplastic material produced from a thermoplastic polymer, a filler, and a chemical blowing agent. Suitable thermoplastic polymer materials include ethylene-methacrylic acid ionomers that have been neutralized by a metal ion and co-polymers of ethylene neutralized with a metal ion, non-neutralized copolymers of ethylene and methacrylic or acrylic acid, polyethylene, and polypropylene.
DE 4015164 discloses embossable foam latex, in pieces or as cut goods, for use in articles, such as sporting goods, golf shoes, golf gloves, and upholstery. A base latex is mixed with a thermoplastic and/or a thermoset polymer, such as a styrene-acrylate copolymer or terpolymer, carboxylated styrene-butadiene copolymer, vinyl acetate homopolymer, copolymer, or terpolymer, and thermoplastic polyurethane.
Several references disclose blends of sulfonated polystyrene ionomers and polyamide-6. For example, R. A. Weiss and X. Lu [Macromol., 25:6185-6189 (1992)] disclose that, in compatible sulfonated ionomer/polyamide blends, a complex forms between the metal sulfonate of a sulfonated polystyrene ionomer and the amide moiety of polyamide-6.
U.S. Pat. No. 4,840,982 discloses a blend containing a matrix of an aromatic polymer (which may be polyamide, polyester, polycarbonate, or polyimide) in which is dispersed an impact modifier consisting of a minor portion of a carboxylated or sulfonated elastomer which is formed into an ionomer. A minor portion of a dispersion stabilizer must also be present. None of the above references, however, mention the utility of such materials in golf equipment.
There is still a need, however, for golf equipment having improved durability due to forming such equipment from polymer compositions comprising ionomeric material containing sulfonated, carboxylated, and/or phosphonated ionomers. Forming golf equipment from at least one sulfonated, carboxylated, and/or phosphonated ionomer can dramatically improve the ability to control the mechanical properties of the composition, including tensile and flexural modulus and impact strength.
The present invention is directed to golf equipment formed at least in part of a composition which comprises at least one ionomer formed from a polymer having at least one moiety selected from the group consisting of sulfonated, carboxylated, or phosphonated acid moieties, and mixtures thereof.
In one embodiment, the ionomer is a reaction product of a metal base and at least one of the sulfonated, carboxylated, phosphonated, or acid moieties. In another embodiment, the metal base comprises at least one metallic cation selected from the group consisting of Li, Na, Zn, Ca, Mg, K, Ti, Zr, W, Mn, Ni, Cu, and Sn. In a further embodiment, from about 1 mol % to about 99 mol % of the moieties of the ionomer are present in an ionic form. In a preferred embodiment, at least about 10 mol % of the moieties of the ionomer are present in an ionic form.
In another embodiment, the polymer is a sulfonated polymer selected from the group consisting of sulfonated thermoplastic elastomers, sulfonated thermoplastic polymers, sulfonated thermoset polymers, and mixtures thereof. Preferably, the sulfonated polymer contains from about 0.1 mol % to about 30 mol % sulfonated moieties. In still another embodiment, the polymer is a sulfonated thermoplastic elastomer having a flexural modulus from about 1,000 psi to about 150,000 psi.
In a further embodiment, the sulfonated thermoplastic elastomer is selected from the group consisting of block copoly(ester-esters); block copoly(ester-ethers); block copoly(amide-esters); block copoly(amide-ethers); block copoly(urethane-esters); block copoly(urethane-ethers); block polystyrene thermoplastic elastomers, ethylene propylene ruber; ethylene-propylene diene terpolymer rubber; a thermoplastic elastomer blend comprising polypropylene and ethylene-propylene-diene terpolymer or ethylene-propylene copolymer rubber wherein the rubber is dynamically vulcanized; and mixtures thereof.
Preferably, the polymer is a sulfonated thermoplastic polymer having a flexural modulus from about 3,000 psi to about 500,000 psi. In another embodiment, the sulfonated thermoplastic polymer is selected from the group consisting of olefinic polymers; polyamides; polyesters; a polystyrene; poly(alkyl)acrylates; polycarbonates; polyphenylene oxide; polyether ketone; polysulfone; poly(phenylene sulfide); poly(ether imide); and mixtures thereof.
Preferably, the polymer is a sulfonated thermoset polymer and wherein the polymer has a flexural modulus from about 1,000 psi to about 150,000 psi. In still another embodiment, the sulfonated thermoset polymer is selected from the group consisting of poly(isoprene); poly(butadiene); poly(octenemer); styrene-butadiene rubber; ethylene-propylene-diene terpolymer rubber; ethylene-propylene copolymer rubber; nitrile rubber; butyl rubber; poly(urethane); poly(urea); poly(siloxane); and mixtures thereof. In a further embodiment, said composition further comprises at least one co-component polymer and wherein the composition comprises a blend of from about 1 weight % to about 99 weight % of said at least one ionomer formed from at least one of the sulfonated, carboxylated, or phosphonated acid moieties, and from about 99 weight % to about 1 weight % of said at least one co-component polymer.
In one embodiment, the co-component polymer is selected from the group consisting of conventional ionomers, non-ionomeric thermoplastic elastomers, non-ionomeric thermoplastic polymers, non-ionomeric thermoset polymers, and mixtures thereof. In a preferred embodiment, the co-component polymer is a non-ionomeric thermoplastic elastomer selected from the group consisting of block copoly(ester-esters); block copoly(ester-ethers); block copoly(amide-esters); block copoly(amide-ethers); block copoly(urethane-esters); block copoly(urethane-ethers); block polystyrene thermoplastic elastomers, ethylene-propylene-diene terpolymer or ethylene-propylene copolymer rubber; a thermoplastic elastomer blend comprising polypropylene and ethylene-propylene-diene terpolymer or ethylene-propylene copolymer rubber wherein the rubber is dynamically vulcanized; and mixtures thereof. In another embodiment, the co-component polymer is a non-ionomeric thermoplastic polymer that comprises at least one olefinic polymer.
In another embodiment, the non-ionomeric thermoplastic polymer is a polyamide polymer having a flexural modulus from about 3,000 psi to about 500,000 psi. Preferably, the polyamide polymer is selected from the group consisting of polyamide homopolymers, polyamide copolymers, and mixtures thereof. In still another embodiment, the polyamide homopolymer is selected from the group consisting of polyamide 6; polyamide 11; polyamide 12; and mixtures thereof. Preferably, the polyamide copolymer is selected from the group consisting of polyamide 4,6; polyamide 6,6; polyamide 6,9; polyamide 6,10; polyamide 6,12; polyamide 6,18; polyamide 6,36; polyamide 6/6,6; polyamide 6,6/6,10; polyamide 6/6,T; polyamide 6/6,6/6,10; polyamide 6/6,6/6,18; polyamide 6/6,6/6,36; and mixtures thereof.
In still another embodiment, the co-component polymer is a thermoplastic polymer selected from the group consisting of poly(amides); poly(ethylene terephthalates); poly(butylene terephthalates); poly(trimethylene terephthalates); poly(ethylene naphthalates); poly(vinyl alcohols); poly(vinyl acetates); poly(silanes); poly(vinylidene fluorides); acrylonitrile-butadiene-styrene copolymers; and mixtures thereof.
In yet another embodiment, the polymer is a carboxylated polymer selected from the group consisting of carboxylated thermoplastic elastomers, carboxylated thermoplastic polymers, carboxylated thermoset polymers, and mixtures thereof.
In a further embodiment, the polymer is a phosphonated polymer selected from the group consisting of phosphonated thermoplastic elastomers, phosphonated thermoplastic polymers, phosphonated thermoset polymers, and mixtures thereof.
In a preferred embodiment, the golf equipment is selected from the group consisting of golf clubs, golf club head additions, club components, golf gloves, golf glove components, golf shoes, golf shoe components, golf bags, golf bag framework, with the proviso that golf balls are specifically excluded from this group. Preferably, the golf equipment is selected from the group consisting of golf clubs, golf shoes, golf gloves, and portions thereof.
The present invention is also directed to a composition comprising at least one ionomer formed from a polymer having at least one moiety selected from the group consisting of sulfonated, carboxylated, or phosphonated acid moieties, and mixtures thereof.
In one embodiment, the ionomer is a reaction product of a metal base and at least one of the sulfonated, carboxylated, phosphonated, or acid moieties. In another embodiment, the metal base comprises at least one metallic cation selected from the group consisting of Li, Na, Zn, Ca, Mg, K, Ti, Zr, W, Mn, Ni, Cu, and Pt. In a further embodiment, from about 1 mol % to about 99 mol % of the moieties of the ionomer are present in an ionic form. In a preferred embodiment, at least about 10 mol % of the moieties of the ionomer are present in an ionic form.
In another embodiment, the polymer is a sulfonated polymer selected from the group consisting of sulfonated thermoplastic elastomers, sulfonated thermoplastic polymers, sulfonated thermoset polymers, and mixtures thereof. Preferably, the sulfonated polymer contains from about 0.1 mol % to about 30 mol % sulfonated moieties. In still another embodiment, the polymer is a sulfonated thermoplastic elastomer having a flexural modulus from about 1,000 psi to about 150,000 psi.
In a further embodiment, the sulfonated thermoplastic elastomer is selected from the group consisting of block copoly(ester-esters); block copoly(ester-ethers); block copoly(amide-esters); block copoly(amide-ethers); block copoly(urethane-esters); block copoly(urethane-ethers); block polystyrene thermoplastic elastomers, ethylene propylene ruber; ethylene-propylene diene terpolymer rubber; a thermoplastic elastomer blend comprising polypropylene and ethylene-propylene-diene terpolymer or ethylene-propylene copolymer rubber wherein the rubber is dynamically vulcanized; and mixtures thereof.
Preferably, the polymer is a sulfonated thermoplastic polymer having a flexural modulus from about 3,000 psi to about 500,000 psi. In another embodiment, the sulfonated thermoplastic polymer is selected from the group consisting of olefinic polymers; polyamides; polyesters; a polystyrene; poly(alkyl)acrylates; polycarbonates; polyphenylene oxide; polyether ketone; polysulfone; poly(phenylene sulfide); poly(ether imide); and mixtures thereof.
Preferably, the polymer is a sulfonated thermoset polymer and wherein the polymer has a flexural modulus from about 1,000 psi to about 150,000 psi. In still another embodiment, the sulfonated thermoset polymer is selected from the group consisting of poly(isoprene); poly(butadiene); poly(octenemer); styrene-butadiene rubber; ethylene-propylene-diene terpolymer rubber; ethylene-propylene copolymer rubber; nitrile rubber; butyl rubber; poly(urethane); poly(urea); poly(siloxane); and mixtures thereof. In a further embodiment, said composition further comprises at least one co-component polymer and wherein the composition comprises a blend of from about 1 weight % to about 99 weight % of said at least one ionomer formed from at least one of the sulfonated, carboxylated, or phosphonated acid moieties, and from about 99 weight % to about 1 weight % of said at least one co-component polymer.
In one embodiment, the co-component polymer is selected from the group consisting of conventional ionomers, non-ionomeric thermoplastic elastomers, non-ionomeric thermoplastic polymers, non-ionomeric thermoset polymers, and mixtures thereof. In a preferred embodiment, the co-component polymer is a non-ionomeric thermoplastic elastomer selected from the group consisting of block copoly(ester-esters); block copoly(ester-ethers); block copoly(amide-esters); block copoly(amide-ethers); block copoly(urethane-esters); block copoly(urethane-ethers); block polystyrene thermoplastic elastomers, ethylene-propylene-diene terpolymer or ethylene-propylene copolymer rubber; a thermoplastic elastomer blend comprising polypropylene and ethylene-propylene-diene terpolymer or ethylene-propylene copolymer rubber wherein the rubber is dynamically vulcanized; and mixtures thereof. In another embodiment, the co-component polymer is a non-ionomeric thermoplastic polymer that comprises at least one olefinic polymer.
In another embodiment, the non-ionomeric thermoplastic polymer is a polyamide polymer having a flexural modulus from about 3,000 psi to about 500,000 psi. Preferably, the polyamide polymer is selected from the group consisting of polyamide homopolymers, polyamide copolymers, and mixtures thereof. In still another embodiment, the polyamide homopolymer is selected from the group consisting of polyamide 6; polyamide 11; polyamide 12; and mixtures thereof. Preferably, the polyamide copolymer is selected from the group consisting of polyamide 4,6; polyamide 6,6; polyamide 6,9; polyamide 6,10; polyamide 6,12; polyamide 6,18; polyamide 6,36; polyamide 6/6,6; polyamide 6,6/6,10; polyamide 6/6,T; polyamide 6/6,6/6,10; polyamide 6/6,6/6,18; polyamide 6/6,6/6,36; and mixtures thereof.
In still another embodiment, the co-component polymer is a thermoplastic polymer selected from the group consisting of poly(amides); poly(ethylene terephthalates); poly(butylene terephthalates); poly(trimethylene terephthalates); poly(ethylene naphthalates); poly(vinyl alcohols); poly(vinyl acetates); poly(silanes); poly(vinylidene fluorides); acrylonitrile-butadiene-styrene copolymers; and mixtures thereof.
In yet another embodiment, the polymer is a carboxylated polymer selected from the group consisting of carboxylated thermoplastic elastomers, carboxylated thermoplastic polymers, carboxylated thermoset polymers, and mixtures thereof.
In a further embodiment, the polymer is a phosphonated polymer selected from the group consisting of phosphonated thermoplastic elastomers, phosphonated thermoplastic polymers, phosphonated thermoset polymers, and mixtures thereof.
The present invention is also directed to a method for forming golf equipment comprising the steps of providing at least one ionomer comprising a polymer having a moiety selected from the group consisting of sulfonated, carboxylated, or phosphonated acid moieties, and mixtures thereof, and forming golf equipment from said at least one ionomer.
As used herein, the term xe2x80x9cgolf equipmentxe2x80x9d includes only golf clubs (i.e., putters, drivers, and wedges) and club attachments, additions, or modifications, such as striking face inserts; golf club components (i.e., shafts, hosels, and grips); golf club vibration damping devices; golf gloves and portions thereof, such as glove liners, securing methods, patches, and reinforcements; golf shoes and associated components (i.e., soles, footbeds and spike socket spines, heel counters, toe xe2x80x9cpuffsxe2x80x9d, uppers, midsoles, outsoles, liners, and plastic golf spikes); golf bags and their associated framework, support legs, and stands; and any portion of the above items, with the proviso that golf balls are specifically excluded from this group.
As used herein, the term xe2x80x9csulfonated, carboxylated, and phosphonated polymersxe2x80x9d is defined as polymers, copolymers, and their precursors, comprising, respectively, sulfonate moieties, carboxylate moieties, phosphonate moieties, derivatives thereof, and mixtures of these polymers and copolymers, including, but not limited to, thermoplastic and thermoset elastomers.
As used herein, in discussing the present invention, the term xe2x80x9cionomers formed from sulfonated, carboxylated, or phosphonated polymersxe2x80x9d are defined as polymers which comprise at least one sulfonic acid, carboxylic acid, or phosphonic acid moiety neutralized with a conjugate base, typically a cation such as a metal ion or a quaternary phosphonium or ammonium cation, and mixtures thereof.
As used herein, the term xe2x80x9cconventional ionomerxe2x80x9d is defined as a polymer which comprises a copolymer of ethylene, an optional softening comonomer which may be present in an amount up to about 50 weight % of the polymer, and selected from among an alkyl acrylate, alkyl methacrylate and mixtures thereof, and an acid present in an amount from about 5 weight % to about 35 weight % of the polymer and selected from the group consisting of acrylic acid, methacrylic acid and mixtures thereof, wherein the acid moiety is neutralized from about 1% to about 90% by at least one said cation.
As used herein, the term xe2x80x9csulfonated polymerxe2x80x9d is intended to include both sulfonated polymers produced by copolymerization with a sulfonated monomer or polymers and copolymers sulfonated by using a sulfonation agent in a post-polymerization reaction.
As used herein, the term xe2x80x9ccarboxylated polymerxe2x80x9d or xe2x80x9ccarboxylatexe2x80x9d are intended to include both carboxylated polymers produced by copolymerization with a carboxylated monomer or polymers and copolymers carboxylated by using a carboxylation agent in a post-polymerization reaction, with the proviso that conventional ionomers, as defined above, are excluded.
As used herein, the term xe2x80x9cphosphonated polymerxe2x80x9d is intended to include both phosphonated polymers produced by copolymerization with a phosphonated monomer or polymers and copolymers phosphonated by using a phosphonation agent in a post-polymerization reaction.
As used herein, a xe2x80x9cnon-ionomeric polymerxe2x80x9d is a polymer or copolymer which comprises substantially no ionic groups, i.e., a polymer or copolymer which is not an ionomer. For example, a non-ionomeric polymer may include a thermoplastic elastomer polymer (xe2x80x9cTPExe2x80x9d), a thermoplastic polymer, a thermoset polymer, or any mixture thereof, none of these materials being ionomers.
As used herein, the term xe2x80x9cco-componentxe2x80x9d is intended to include polymers selected from the group consisting of conventional ionomers, non-ionomeric thermoplastic elastomers, non-ionomeric thermoplastic polymers, non-ionomeric thermoset polymers, and mixtures and precursors thereof.